A Modified Approach for in Situ Chemical Oxidation Coupled to Biodegradation Enhances Light Nonaqueous Phase Liquid Source-Zone Remediation

Fedrizzi, Franciele; Ramos, Débora Toledo; Lazzarin, Helen Simone Chiaranda; Fernandes, Marilda; Larose, Catherine; Vogel, Timothy M.; Corseuil, Henry Xavier

doi:10.1021/acs.est.6b03604

Cited by 16 publications

(1 citation statement)

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“…Oxidative processes play an important role in pollutant degradation in natural , and numerous engineered systems, such as during the remediation of contaminated sites − and water treatment processes . In water treatment processes, a broad variety of oxidants are used, including chlorine dioxide (ClO 2 ), , ozone (O 3 ), , and hydroxyl radicals ( • OH) .…”

Section: Introductionmentioning

confidence: 99%

Carbon Isotope Fractionation of Substituted Benzene Analogs during Oxidation with Ozone and Hydroxyl Radicals: How Should Experimental Data Be Interpreted?

Willach

Lutze

Somnitz

et al. 2020

Environ. Sci. Technol.

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Oxidative processes frequently contribute to organic pollutant degradation in natural and engineered systems such as during the remediation of contaminated sites and in water treatment processes. Because a systematic characterization of abiotic reactions of organic pollutants with oxidants such as ozonation or hydroxyl radicals by compound-specific stable isotope analysis (CSIA) is lacking, stable isotope-based approaches have rarely been applied for the elucidation of mechanisms of such transformations. Here, we investigated the carbon isotope fractionation associated with the oxidation of benzene and several methylated and methoxylated analogs, namely toluene, three xylene isomers, mesitylene and anisole, and determined their carbon isotope enrichments factors (εC) for reactions with ozone (εC = −3.6 ‰ to −4.6 ‰) and hydroxyl radicals (εC = 0.0 to −1.2 ‰). The differences in isotope fractionation can be used to elucidate the contribution of the reactions with ozone or hydroxyl radicals to overall transformation. Derivation of apparent kinetic isotope effects (AKIEs) for the reaction with ozone, however, was nontrivial due to challenges in assigning reactive positions in the probe compounds for the monodentate attack leading to an ozone adduct. We present several options for this step and compare the outcome to quantum chemical characterizations of ozone adducts.Our data show that a general assignment of reactive positions for reactions of ozone with aromatic carbon in ortho-, metaor para-positions is not feasible and that AKIEs of this reaction should be derived on a compound-by-compound basis.

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